Absorbent, CO2 or H2S reducing apparatus, and CO2 or H2S reducing method using absorbent

ABSTRACT

An absorbent according to the present invention absorbs CO 2  or H 2 S contained in flue gas emitted from a power generating plant such as a thermal plant, and contains three or more amine compounds selected from linear or cyclic amine compounds having a primary amino group, and linear or cyclic amine compounds having a secondary amino group. By way of a synergetic effect of the mixture of these compounds, the absorption speed of CO 2  or H 2 S absorption is improved. A small amount of CO 2  contained in a large amount of boiler flue gas can be absorbed efficiently.

TECHNICAL FIELD

The present invention relates to an absorbent that reduces CO₂ (carbon dioxide) or H₂S (hydrogen sulfide) contained in gas such as combustion flue gas, and to a CO₂ or H₂S reducing apparatus and a CO₂ or H₂S reducing method using the absorbent.

BACKGROUND ART

It has come to be pointed out that one of the causes of the global warming is a greenhouse effect of CO₂, and it has became an urgent task, also internationally, to provide a countermeasure for CO₂ to protect the global environment against the warming. CO₂ is generated by any human activities combusting fossil fuels, and there are increasing demands for suppressing CO₂ emissions. Along with such an increasing demand, researches are energetically investing a method for reducing and collecting CO₂ in combustion flue gas, and storing therein collected CO₂ without releasing it to the air, by bringing combustion flue gas emitted from a steam generator in contact with aqueous alkanolamine solution and the like, for applications in a power plant that consumes a large amount of fossil fuels, such as a thermal plant. In addition, it has been suggested that the aqueous alkanolamine solution can reduce acid gas such as H₂S (hydrogen sulfide), as well as CO₂ (carbon dioxide).

Examples of the alkanolamines include monoethanolamine (MEA), triethanolamine (TEA), N-methyldiethanolamine (MDEA), diisopropanolamine (DIPA), and diglycolamin (DGA), and usually monoethanolamine (MEA) is preferably used. In addition, it has been suggested to use a cyclic amine such as piperazine as an auxiliary absorbing agent in these alkanolamines (Patent Document 1).

-   [Patent Document 1] U.S. Pat. No. 3,233,809 -   [Patent Document 2] Japanese Patent Application Laid-open No.     H06-343858 -   [Patent Document 3] Japanese Patent Application Laid-open No.     H08-257354 -   [Patent Document 4] Japanese Patent Application Laid-open No.     H08-252430 -   [Patent Document 5] Japanese Patent Application Laid-open No.     H06-343858

DISCLOSURE OF INVENTION Problem to be Solved by the Invention

To efficiently collect CO₂ or H₂S contained in a large volume of flue gas emitted from a steam generator in a large turbine facility and the like, there is a demand for an absorbent having a CO₂ or H₂S absorption speed as high as possible.

In response to this issue, it has been suggested to employ a primary amine having a high absorption speed, together with another additive component to obtain a binary absorbent (Patent Documents 2 and 3). It has also been suggested to obtain a binary absorbent consisting of a secondary amine and a tertiary amine (Patent Document 4). However, either of these absorbent is not in practical use yet.

Tertiary amine is suggested to use for ternary absorbent (Patent Document 5). This absorbent is for absorbing and reducing a relatively large quantity of CO₂ or H₂S contained in natural gas, heavy oil synthesis gas, or oil refinery gas. In addition, the CO₂ absorption speed of a tertiary amine is low. Thus, there is a problem from a perspective of a practical use of efficiently reducing CO₂ or H₂S existing in a low concentration in flue gas emitted from a steam generator in a large turbine facility and the like.

In consideration of the above, an object of the present invention is to provide an absorbent that can dramatically improve the reduction speed of CO₂ or H₂S contained in combustion flue gas, further to improve CO₂ or H₂S reduction efficiency, and to provide a CO₂ or H₂S reducing apparatus and a CO₂ or H₂S reducing method using such an absorbent.

Means for Solving Problem

According to an aspect of the present invention, an absorbent that absorbs CO₂ or H₂S contained in gas, the absorbent comprising three or more amine compounds selected from linear or cyclic amine compounds having a primary amino group, and linear or cyclic amine compounds having a secondary amino group.

Advantageously, in the absorbent, the three amine compounds includes two amine compounds selected from linear amine compounds having a primary amino group or linear amine compounds having a secondary amino group, and a cyclic amine compound having a primary or a secondary amino group.

Advantageously, in the absorbent, the three amine compounds includes two amine compounds including one compound selected from linear amine compounds having a primary amino group and another compound selected from linear amine compounds having a secondary amino group, and a cyclic amine compound having a primary or a secondary amino group.

Advantageously, in the absorbent, the three amine compounds includes two amine compounds selected from linear amine compounds having a secondary amino group, and a cyclic amine compound having a primary or a secondary amino group.

Advantageously, in the absorbent, a compounding ratio of the three amine compounds is: 2-n-butylaminoethanol (n-BAE) or 2-ethylaminoethanol (EAE) used as a main component accounting for 30 to 55 weight percent; two amine compounds selected from linear or cyclic amine compounds having a primary amino group, and linear or cyclic amine compounds having a secondary amino group used as minor components accounting for 1 to 30 weight percent; and water accounting for the remaining weight percent.

Advantageously, in the absorbent, a compounding ratio of the three amine compounds is: 2-n-butylaminoethanol (n-BAE) or 2-ethylaminoethanol (EAE) used as a main component accounting for 30 to 55 weight percent; two amine compounds selected from linear or cyclic amine compounds having a primary amino group, and linear or cyclic amine compounds having a secondary amino group used as minor components accounting for 1 to 30 weight percent; and water accounting for the remaining weight percent, and two amine compounds include: a linear or cyclic amine compound having a primary amino group used as a first minor component accounting for 15 to 5 weight percent; and two amine compounds selected from linear or cyclic amine compounds having a secondary amino group used as second minor components accounting for 10 to 1 weight percent; and the water accounting for the remaining weight percent.

Advantageously, in the absorbent, a compounding ratio of the three amine compounds is: 2-n-butylaminoethanol (n-BAE) or 2-ethylaminoethanol (EAE) used as a main component accounting for 30 to 55 weight percent; two amine compounds selected from linear or cyclic amine compounds having a primary amino group, and linear or cyclic amine compounds having a secondary amino group used as minor components accounting for 1 to 30 weight percent; and water accounting for the remaining weight percent, and the two amine compounds includes two selected from piperazine (P), methylpiperazine (MP), hydroxyethylpiperazine (HEP), monoethanolamine (MEA), diethanolamine (DEA), diisopropanolamine (DIPA), diglycolamin (DGA), 3-amino-1-propanol (AP), 2-amino-2-methylpropanol (AMP), 2-methylaminoethanol (MAE), 2-ethylaminoethanol (EAE), 2-n-propylaminoethanol (n-PAE), 2-n-butylaminoethanol (n-BAE), 2-isopropylaminoethanol (i-PAE), 2-isobutylaminoethanol (i-BAE), 1-(2-aminoethyl)piperazine (AEPRZ), and piperidinol (PDN).

Advantageously, in the absorbent, a compounding ratio of the three amine compounds is: 2-n-butylaminoethanol (n-BAE) or 2-ethylaminoethanol (EAE) used as a main component accounting for 30 to 55 weight percent; two amine compounds selected from linear or cyclic amine compounds having a primary amino group, and linear or cyclic amine compounds having a secondary amino group used as minor components accounting for 1 to 30 weight percent; and water accounting for the remaining weight percent, and the two amine compounds include: a linear or a cyclic amine compound having a primary amino group used as a first minor component accounting for 15 to 5 weight percent; two amine compounds selected from linear or cyclic amine compounds having a secondary amino group used as second minor components accounting for 10 to 1 weight percent; and the water accounting for the remaining weight percent, and the two amine compounds includes two selected from piperazine (P), methylpiperazine (MP), hydroxyethylpiperazine (HEP), monoethanolamine (MEA), diethanolamine (DEA), diisopropanolamine (DIPA), diglycolamin (DGA), 3-amino-1-propanol (AP), 2-amino-2-methylpropanol (AMP), 2-methylaminoethanol (MAE), 2-ethylaminoethanol (EAE), 2-n-propylaminoethanol (n-PAE), 2-n-butylaminoethanol (n-BAE), 2-isopropylaminoethanol (i-PAE), 2-isobutylaminoethanol (i-BAE), 1-(2-aminoethyl)piperazine (AEPRZ), and piperidinol (PDN).

According to another aspect of the present invention, a CO₂ or H₂S reducing apparatus that reduces CO₂ or H₂S contained in gas, includes: an absorber that brings gas containing CO₂ or H₂S into contact with absorbent to reduce CO₂ or H₂S contained in the gas; and a regenerator that recycles a solvent that has absorbed CO₂ or H₂S. The solvent having CO₂ or H₂S reduced and recycled in the regenerator is reused in the absorber, and the absorbent described above is used.

According to still another aspect of the present invention, a CO₂ or H₂S reducing method that reduces CO₂ or H₂S contained in gas by using an absorber that brings gas containing CO₂ or H₂S into contact with absorbent to reduce CO₂ or H₂S contained in the gas and a regenerator that recycles a solvent that has absorbed CO₂ or H₂S so that the solvent having CO₂ or H₂S reduced and recycled in the regenerator is reused in the absorber, the CO₂ or H₂S reducing method includes: Using the absorbent described above.

The gas containing CO₂ or H₂S is preferably combustion flue gas emitted from a combustion facility (such as a steam generator).

Effect of the Invention

According to the present invention, as an amine compound that absorbs one of CO₂ and H₂S or both contained in gas, an amine compound contains three or more amine compounds selected from linear or cyclic amine compounds having a primary amino group, linear or cyclic amine compounds having a secondary amino group. Therefore, an excellent CO₂ or H₂S reducing performance is achieved.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic of a CO₂ reducing apparatus.

EXPLANATIONS OF LETTERS OR NUMERALS

-   -   1 absorber     -   15 regenerator

BEST MODE(S) FOR CARRYING OUT THE INVENTION

The present invention will now be explained in detail with reference to the drawing. It should be understood that an embodiment of the present invention is not intended to limit the scope of the present invention in any way. Furthermore, the embodiment shall be construed to include structural elements that can be easily imagined by those in the art, or those that are substantially identical.

Embodiment of Present Invention

An absorbent according to the present invention is one that absorbs CO₂ or H₂S contained in flue gas (hereinafter, “gas”) emitted from a power generating plant such as a thermal plant, and contains three or more amine compounds selected from linear or cyclic amine compounds having a primary amino group, and linear or cyclic amine compounds having a secondary amino group.

Examples of the linear or the cyclic amine compounds having a primary amino group include mono-n-butylamine (MBA), monoethylamine (MEA), n-propanolamine (NPA), 2-amino-2-methylpropanol (AMP), and diglycolamin (DGA).

Examples of the linear or the cyclic amine compounds having a secondary amino group include 2-methylaminoethanol (MAE), 2-ethylaminoethanol (EAE), 2-n-propylaminoethanol (n-PAE), 2-n-butylaminoethanol (n-BAE), 2-isopropylaminoethanol (i-PAE), 2-isobutylaminoethanol (i-BAE), piperazine (P), 2-methylpiperazine (MP), 1-(2-aminoethyl)piperazine (AEPRZ), and piperidinol (PDN).

The three amine compounds preferably include two amine compounds selected from linear amine compounds having a primary amino group, and linear amine compounds having a secondary amino group, and a cyclic amine compound having a primary or a secondary amino group.

The three amine compounds preferably include two amine compounds having a compound selected from linear amine compounds having a primary amino group and another compound selected from linear amine compounds having a secondary amino group, and a cyclic amine compound having a primary or a secondary amino group.

The three amine compounds preferably include two amine compounds selected from linear amine compounds having a secondary amino group, and a cyclic amine compound having a primary or a secondary amino group.

An especially preferable combination includes a combination of one selected from MEA and AMP as the linear amine compound having a primary amino group; one selected from MAE, EAE, and BAE as the linear amine compounds having a secondary amino group; and one selected from P, MP, and AEPRZ as the cyclic amine compounds having a primary or a secondary amino group.

Compounding ratio of the three amine compounds, it is preferable to use 2-n-butylaminoethanol (n-BAE) or 2-ethylaminoethanol (EAE) as a main component that accounts for 30 to 55 weight percent; and to use two amine compounds selected from linear or cyclic amine compounds having a primary amino group, and linear or cyclic amine compounds having a secondary amino group as minor components that account for 1 to 30 weight percent; and to use water for the remaining weight percent. Furthermore, MEA (primary amine compound), AMP (primary amine compound), and MAE (secondary amine compound) may be used as the main component. In addition, it is preferable to use MEA, AMP, and the like also as the minor component.

Furthermore, preferably, the two amine compounds that are the minor components include a first minor component and a second minor component; and a linear or a cyclic amine compound having a primary amino group is used as the first minor component accounting for 15 to 5 weight percent; two amine compounds selected from linear or cyclic amine compounds having a secondary amino group are used as the second minor components accounting for 10 to 1 weight percent; and the remaining weight percent is water.

Preferably, the two amine compounds are, for example, two selected from piperazine (P), methylpiperazine (MP), hydroxyethylpiperazine (HEP), monoethanolamine (MEA), diethanolamine (DEA), diisopropanolamine (DIPA), diglycolamin (DGA), 3-amino-1-propanol (AP), 2-amino-2-methylpropanol (AMP), 2-methylaminoethanol (MAE), 2-ethylaminoethanol (EAE), 2-n-propylaminoethanol (n-PAE), 2-n-butylaminoethanol (n-BAE), 2-isopropylaminoethanol (i-PAE), 2-isobutylaminoethanol (i-BAE), 1-(2-aminoethyl)piperazine (AEPRZ), and piperidinol (PDN).

If 2-ethylaminoethanol (EAE) is used as the main component, it is especially preferable to use two out of piperazine (P), 1-(2-aminoethyl)piperazine (AEPRZ), methylpiperazine (MP), 2-amino-2-methylpropanol (AMP), and piperidinol (PDN) as the minor components.

If 2-ethylaminoethanol (EAE) is used as the main component, it is especially preferable to use two out of piperazine (P), 1-(2-aminoethyl)piperazine (AEPRZ), and 2-amino-2-methylpropanol (AMP) as the minor components.

The component other than amines is usually water; however, other solvent or mixture of water and other solvent may also be used. Furthermore, corrosion inhibitor, antidegrant, and the like are added as required.

According to the present invention, the temperature of the absorbent when the liquid is brought into contact with gas is usually in a range of 30 to 70 Celsius degrees.

Applicable gas conditions for the present invention are represented by a total pressure of approximately atmospheric pressure and CO₂ concentration of 10 percent; however, such conditions are not limited thereto.

Examples of gas processed by the present invention include, for example, coal gasification gas, synthesis gas, coke oven gas, petroleum gas, or natural gas; however, these examples are not limited thereto, and the present invention is applicable to any gas containing acid gas such as CO₂ or H₂S.

No special limitation is set to a process that can be used for a method for reducing any one of CO₂ and H₂S or both according to the present invention. An exemplary reducing apparatus for reducing CO₂ will now be explained with reference to FIG. 1.

FIG. 1 is a schematic of the CO₂ reducing apparatus. As shown in FIG. 1, gas is guided through a CO₂-containing gas supplying opening 4 into an absorber 1. The gas confined in the absorber 1 is brought in a counter-current contact with CO₂ absorbent supplied from a nozzle 7 in a filler 2. CO₂ included in the gas is absorbed and reduced by the absorbent, and the gas is ejected from a CO₂-reduced gas ejecting opening 5. The absorbent supplied to the absorber 1 absorbs CO₂, sent to a heat exchanger 14 and a heater 8 to be heated, and further sent to the regenerator 15. In the regenerator 15, the absorbent goes through a nozzle 16 and a filler 17, and flows downwardly. During this time, CO₂ becomes desorbed, and the absorbent is rejuvenated. The rejuvenated absorbent is caused to go through the heat exchanger 14 and an absorbent cooler 26 by way of a pump 9, and fed back to the absorber 1 through an absorbent supplying opening 6. The CO₂ desorbed from the absorbent is brought in contact with refluxing water supplied from a nozzle 18 at the upper area of the regenerator 15, and cooled in a regenerator reflux cooler 23. In a reflux drum 21, the steam that accompanies CO₂ is separated from condensed refluxing water, and guided to a CO₂ collection process by way of a collected CO₂ line 22. The refluxing water is sent to the regenerator 15 by way of a refluxing water pump 20. In this embodiment, only a general structure is described, and auxiliary equipment is partially omitted in the description.

By using the absorbent according to the present invention as the absorbent in the CO₂ reducing apparatus, CO₂ can be absorbed and reduced efficiently.

Embodiment

The present invention will now be explained in detail based on an embodiment of the present invention.

According to the embodiment, as shown in Table 1, when 2-n-butylaminoethanol (n-BAE) is used as a main component, two out of piperazine (P), 1-(2-aminoethyl)piperazine (AEPRZ), methylpiperazine (MP), 2-amino-2-methylpropanol (AMP), and piperidinol (PDN) are used as minor components to produce each of the absorbents.

As shown in Table 1, when 2-ethylaminoethanol (EAE) is used as a main component, two out of piperazine (P), 1-(2-aminoethyl)piperazine (AEPRZ), and 2-amino-2-methylpropanol (AMP) are used as minor components to produce each of the absorbents.

As comparative examples, a binary combination of 2-ethylaminoethanol (EAE) and 1-(2-aminoethyl)piperazine (AEPRZ) (comparative example 1), a combination of diethanolamine (DEA) and piperazine (P) (comparative example 2), and a ternary system using tertiary amine with a combination of hydroxyethylpiperazine (HEP), piperazine (P), and methyldiethanolamine (MDEA) (comparative example 3) are produced as absorbents.

In the table, the numbers in parenthesis represent weight percent.

In the second column of the table, “Molar Content per 1.4 Mol” indicates a ratio of a weight percent converted into M (Mol/liter), so that the sum of each of the components becomes 1.4 mol.

In third column of the table, “Singular Performance in Amount Corresponding to Content” indicates (singular performance at 1.4 mol)+1.4×(molar content).

In fourth column of the table, “Linear Prediction” is the sum of the singular performance of each of the components in the amount corresponding to the content, without giving any consideration to interaction.

In sixth column of the table, “Synergetic Effect” indicates a quantity of synergetic effect calculated by subtracting the linear prediction from the compound liquid measured, and a synergetic effect (percent) is calculated by (the quantity of synergetic effect)+(linear prediction)×100.

<Test Description>

To obtain an exact reaction speed between the absorbent and CO₂, a flat-contact churn type testing apparatus (inner diameter: 11.5 centimeters, gas contact area: 91.61 square centimeters, bathing temperature: 25 Celsius degrees) having churn blades in a basin was used. An absorption speed was measured for each of the absorbents, while the partial pressure of gas-phase CO₂ was changed respectively at a constant speed while maintaining an amine concentration constant.

For the analysis of CO₂ concentration, an infrared CO₂ analyzer was used.

The results are indicated in Table 1, as a synergetic effect of the mixtures expressed by a square root of a reaction speed constant (m³/kmol·s).

TABLE 1 Synergetic Singular Performance in Linear Compound Effect Molar Content per 1.4 Amount corresponding to Prediction Liquid Quantity % Mol *1 Content *2 *3 Measured *4 *5 TEST-1 BAE(40) + n-BAE P AEPRZ n-BAE P AEPRZ 75.3 92.8 17.5 23.3 P(9) + AEPRZ(3) 1.019 0.321 0.069 46.1 24.5 4.7 TEST-2 n-BAE(40) + n-BAE P MP n-BAE P MP 76.5 90.4 13.9 18.1 P(9) + MP(6) 0.945 0.289 0.166 42.7 22.7 11.1  TEST-3 n-BAE(40) + n-BAE P AMP n-BAE P AMP 67.2 89.8 22.6 33.5 P(9) + AMP(6) 0.931 0.285 0.184 42.1 22.4 2.7 TEST-4 n-BAE(40) + n-BAE P PDN n-BAE P PDN 76.9 86.7 9.8 12.8 P(9) + PDN(6) 0.946 0.290 0.164 42.8 22.8 11.3  TEST-5 EAE(40) + EAE P AEPRZ EAE P AEPRZ 77.4 84.8 7.4 9.6 P(9) + AEPRZ(3) 1.090 0.254 0.056 53.6 19.9 3.8 TEST-6 EAE(40) + EAE AMP P EAE AMP P 62.3 71.3 9.0 14.5 AMP(10) + P(3) 1.055 0.264 0.082 51.9  3.9 6.4 TEST-7 EAE(40) + EAE AMP AEPRZ EAE AMP AEPRZ 60.7 65.8 5.1 8.4 AMP(10) + AEPRZ(3) 1.075 0.269 0.056 52.9  4.0 3.8 TEST-8 BAE(40) + n-BAE AMP AEPRZ n-BAE AMP AEPRZ 54.9 63.9 9.0 16.5 AMP(10) + AEPRZ(3) 1.002 0.329 0.068 45.3  4.9 4.6 TEST-9 BAE(40) + n-BAE AMP P n-BAE AMP P 56.9 60.9 4.0 7.0 AMP(10) + P(3) 0.979 0.322 0.100 44.2  4.8 7.8 COMPARATIVE-1 EAE(50) + EAE AEPRZ — EAE AEPRZ — 69.9 68.8 −1.0 −1.5 AEPRZ(3) 1.344 0.056 66.2  3.8 COMPARATIVE-2 DEA(50) + DEA P — DEA P — 29.5 — — — P(3) 1.283 0.117 20.2  9.2 COMPARATIVE-3 HEP(50) − HEP P MDEA HEP P MDEA 29.5 — — — P(5) + MDEA(30) 0.154 0.233 1.012  7.9 18.3 3.2 *1 M(mol/liter) conversion of a ratio of the weight percent (The sum of the components is 1.4M.) *2 (Singular performance at 1.4M) ÷ 1.4 × (Molar content) *3 The sum of singular performance of each of the components in the amount corresponding to the content (without interaction) *4 (Compound liquid measured) − (Linear prediction) *5 (Synergetic effect) ÷ (Linear prediction) × 100

As shown in Table 1, in all of test examples 1 to 9, linear predictions were approximately equal to or higher than 55, and all of the actual measurements with the compound liquids greatly exceeded the linear predictions, allowing us to confirm the synergetic effect of the ternary system.

On the contrary, in the comparative example 1, the linear prediction was approximately 70; however, the actual measurement with the compound liquid did not score high, not allowing us to obtain the synergetic effect.

Furthermore, for the comparative examples 2 and 3, the linear predictions were equal to or less than 30; therefore, the synergetic effect cannot be expected.

In Table 1, we confirmed that we can especially expect a great synergetic effect in the ternary absorbent of the test example 3 consisting of a combination of n-BAE, P, and AMP. The results were good as well when MP or AEPRZ was used instead of P.

INDUSTRIAL APPLICABILITY

As described above, the absorbent according to the present invention improves the CO₂ absorption speed. Therefore, a small amount of CO₂ contained in a large amount of boiler flue gas can be absorbed efficiently. Thus, the absorbent according to the present invention is suitable for processing flue gas emitted from a plant facility such as various types of steam generators. 

The invention claimed is:
 1. An absorbent that absorbs CO₂ or H₂S contained in gas, the absorbent consisting essentially of: a main component which is 2-n-butylaminoethanol (n-BAE); minor components selected from any two of piperazine (P), 1-(2-aminoethyl)piperazine (AEPRZ), 2-amino-2-methylpropanol (AMP), and piperidinol (PDN); and water, wherein the main component accounts for 30 to 55 weight percent, the minor components account for 20 to 1 weight percent, and the water accounts for the remaining weight percent.
 2. A CO₂ or H₂S reducing apparatus that reduces CO₂ or H₂S contained in gas, the CO₂ or H₂S reducing apparatus comprising: an absorber that brings gas containing CO₂ or H₂S into contact with absorbent to reduce CO₂ or H₂S contained in the gas; and a regenerator that recycles a solvent that has absorbed CO₂ or H₂S, wherein the solvent having CO₂ or H₂S reduced and recycled in the regenerator is reused in the absorber, and the absorbent according to claim 1 is used.
 3. A CO₂ or H₂S reducing method comprising: reducing CO₂ or H₂S in gas by bringing the gas containing CO₂ or H₂S into contact with absorbent, and recycling a solvent that has absorbed CO₂ or H₂S so that the solvent having CO₂ or H₂S reduced and recycled is reused, wherein the absorbent according to claim 1 is used as the absorbent. 